Synthesis and assessment of compounds trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine as hosts for potential xylene and ethylbenzene guests

  • Benita BartonEmail author
  • Daniel V. Jooste
  • Eric C. Hosten
Original Article


In this work, two novel compounds, trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine 1 and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine 2, were designed and successfully synthesized in our laboratories, and assessed for their host potential in the presence of potential xylene (Xy) isomer and ethylbenzene (EB) guests. Host 1 successfully formed complexes with all four of o-Xy, m-Xy, p-Xy and EB, while 2 only clathrated p-Xy and EB. Equimolar guest/guest competition experiments showed that hosts 1 and 2 possess very similar selectivities for these guests [p-Xy (73.9%) > EB (13.0%) > m-Xy (8.1%) > o-Xy (5.0%) and p-Xy (71.3%) > EB (20.2%) > m-Xy (6.0%) > o-Xy (2.5%) for 1 and 2, respectively]. Single crystal diffraction analyses revealed striking geometry changes for the sulfur host analogue: while the tricyclic fused ring system of the oxygen host remained planar when guest was absent or present, this fused system of the sulfur analogue experienced a dramatic geometry change from buckled (in the absence of guest) to planar (in guest presence). This observation explained the selectivity similarities of both hosts in the presence of these guests. Additionally, the relative thermal stabilities of the four complexes with host 1 were assessed by employing thermal analyses, and the results of these correlated exactly with the selectivity order, since the onset temperature of the guest release processes (Ton) was in the order p-Xy (88.0 °C) > EB (70.9 °C) > m-Xy (59.7 °C) > o-Xy (46.2 °C). Ton values also explained the significant preference of host 2 for p-Xy (115.5 °C) relative to EB (76.6 °C), respectively.


Xylene Ethylbenzene Host–guest chemistry Supramolecular chemistry Xanthenyl systems 



Financial support is acknowledged from the Nelson Mandela University and the National Research Foundation (NRF).

Supplementary material

10847_2019_883_MOESM1_ESM.docx (549 kb)
Supplementary material Crystallographic data for both the novel host materials 1 and 2 as well as the six complexes were deposited at the Cambridge Crystallographic Data Centre (CCDC reference numbers 1: 1876416, 2: 1876417, 1·o-Xy: 1876418, 1·m-Xy: 1876419, 1·p-Xy: 1876420, 1·EB: 1876421, 2·p-Xy: 1876422 and 2·EB: 1876423). The Supplementary information contains more comprehensive tables that summarize the various host−host and host−guest interactions for hosts 1 (Table S1) and 2 (Table S2), as well as relevant 1H-NMR, 13C-NMR and IR spectra (Figures S1−S16). (DOCX 549 KB)


  1. 1.
    Atwood, J.L., Steed, J.W.: Encyclopedia of supramolecular chemistry, CRC Press, vol. 1. Marcel Dekker, Inc., New York (2004)CrossRefGoogle Scholar
  2. 2.
    Steed, J.W., Atwood, J.L.: Supramolecular chemistry. Wiley, New York (2009)CrossRefGoogle Scholar
  3. 3.
    Seebach, D., Beck, A.K., Heckel, A.: TADDOLs, their derivatives, and TADDOL analogues: versatile chiral auxiliaries. Angew. Chem., Int. Ed. 40, 92 (2001)CrossRefGoogle Scholar
  4. 4.
    Lusi, M., Barbour, L.J.: Angew. Chem. Int. Ed. Engl. 51, 3928 (2012)Google Scholar
  5. 5.
    Huang, D., Wu, D.: Biodegradable dendrimers for drug delivery. Mater. Sci. Eng. C 90, 713 (2018)CrossRefGoogle Scholar
  6. 6.
    Iskierko, Z., Noworyta, K., Piyush, S.S.: Molecular recognition by synthetic receptors: application in field-effect transistor based chemosensing. Biosens. Bioelectron. 109, 50 (2018)CrossRefGoogle Scholar
  7. 7.
    Cai, H., Huang, Y., Li, D.: Biological metal–organic frameworks: structures, host–guest chemistry and bio-applications. Coord. Chem. Rev.
  8. 8.
    Manandhar, E., Wallace, K.J.: Host–guest chemistry of pyrene-based molecular receptors. Inorg. Chim. Acta 381, 15 (2012)CrossRefGoogle Scholar
  9. 9.
    Nassimbeni, L.R., Marivel, S., Su, H., Weber, E.: Inclusion of picolines by a substituted binaphthyl diol host: selectivity and structure. RSC. Adv. 3, 25758 (2013)CrossRefGoogle Scholar
  10. 10.
    Seo, C.H., Kim, Y.H.: Separation of ethylbenzene and p-xylene using extractive distillation with p-dinitrobenzene. Sep. Purif. Technol. 209, 1 (2019)CrossRefGoogle Scholar
  11. 11.
    Yang, H., Hu, Y.: Separation of para-xylene and meta-xylene by extraction process using aqueous cyclodextrins solution. Chem. Eng. Process. 116, 114 (2017)CrossRefGoogle Scholar
  12. 12.
    Hong, S., Kim, D., Richter, H., Moon, J., Choi, J.: Quantitative elucidation of the elusive role of defects in polycrystalline MFI zeolite membranes on xylene separation performance. J. Membr. Sci. 569, 91 (2019)CrossRefGoogle Scholar
  13. 13.
    Khabzina, Y., Laroche, C., Perez-Pellitero, J., Farrusseng, D.: Xylene separation on a diverse library of exchanged faujasite zeolites. Microporous Mesoporous Mater. 247, 52 (2017)CrossRefGoogle Scholar
  14. 14.
    Hasan, M.M.F., First, E.L., Floudas, C.A.: Discovery of novel zeolites and multi-zeolite processes for p-xylene separation using simulated moving bed (SMB) chromatography. Chem. Eng. Sci. 159, 3 (2017)CrossRefGoogle Scholar
  15. 15.
    Gao, B., Huang, M., Zhang, Z., Yang, Q., Bao, Z.: Hybridization of metal–organic framework and monodisperse spherical silica for chromatographic separation of xylene isomers. Chin. J. Chem. Eng.
  16. 16.
    Belarbi, H., Boudjema, L., Shepherd, C., Ramsahye, N., Trens, P.: Adsorption and separation of hydrocarbons by the metal organic framework MIL-101(Cr). Colloids. Surf. A 520, 46 (2017)CrossRefGoogle Scholar
  17. 17.
    Ma, Y., Zhang, F., Yang, S., Lively, R.P.: Evidence for entropic diffusion selection of xylene isomers in carbon molecular sieve membranes. J. Membr. Sci. 564, 404 (2018)CrossRefGoogle Scholar
  18. 18.
    Kawahata, M., Hyodo, T., Tominaga, M., Yamaguchi, K.: Separation of p-xylene from aromatic compounds through specific inclusion by acyclic host molecule. CrystEngComm. 20, 5667 (2018)CrossRefGoogle Scholar
  19. 19.
    Barton, B., Caira, M.R., de Jager, L., Hosten, E.C.: N,N′-Bis(9-phenyl-9-thioxanthenyl)ethylenediamine: highly selective host behavior in the presence of xylene and ethylbenzene guest mixtures. Cryst. Growth Des. 17, 6660 (2017)CrossRefGoogle Scholar
  20. 20.
    Barton, B., de Jager, L., Hosten, E.C.: An investigation of the complexation of host N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine with dihaloalkanes guests. J. Incl. Phenom. Macrocycl. Chem. 89, 105 (2017)CrossRefGoogle Scholar
  21. 21.
    Barton, B., Jager, L., Hosten, E.C.: A comparison of the behaviour of two closely related xanthenyl-derived host compounds in the presence of vaporous dihaloalkanes. J. Incl. Phenom. Macrocycl. Chem. 92, 181 (2018)CrossRefGoogle Scholar
  22. 22.
    Barton, B., de Jager, L., Hosten, E.C.: Host proficiency of N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine for pyridine and the methylpyridine guests—a competition study. Supramol. Chem. 30, 61 (2018)CrossRefGoogle Scholar
  23. 23.
    Bruker, A.X.S.: APEX2, SADABS and SAINT. Bruker, A.X.S., Madison (2010)Google Scholar
  24. 24.
    Sheldrick, G.M.: SHELXT—integrated space-group and crystal-structure determination. Acta Crystallogr. A71, 3 (2015)Google Scholar
  25. 25.
    Sheldrick, G.M.: SHELXT—integrated space-group and crystal-structure determination. Acta Crystallogr. C71, 3 (2015)Google Scholar
  26. 26.
    Hübschle, C.B., Sheldrick, G.M., Dittrich, B.: ShelXle: a Qt graphical user interface for SHELXL. J. Appl. Crystallogr. 44, 1281 (2011)CrossRefGoogle Scholar
  27. 27.
    Barton, B., McCleland, C.W., Taljaard, B.: The synthesis of novel enclathration compounds: bis(9-amino-9-aryl-9H-thioxanthenes) and investigations of their host-guest potential. S. Afr. J. Chem. 55, 144 (2002)Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Department of ChemistryNelson Mandela UniversityPort ElizabethSouth Africa

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